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William H. Brown William H. Brown Christopher S. Foote Christopher S. Foote Brent L. Iverson Brent L. Iverson
6-1
Reactions of Alkenes
Chapter 6
6-2
Characteristic Reactions
Reaction
DescriptiveName(s)
+
C C
C C
C C
+ Br2
(X2 ) H2 O
Bromination (halogenation)
C C
+ Br2
(X2 )
6-3
Characteristic Reactions
C C
+ Hg(OAc) 2
H2 O
C C
BH3
C C
+ OsO4
C C
H2
6-4
Reaction Mechanisms
x
6-5
Gibbs free energy change, G0: a thermodynamic function relating enthalpy, entropy, and temperature
G0 =H0 TS0
exergonic reaction: a reaction in which the Gibbs free energy of the products is lower than that of the reactants; the position of equilibrium for an exergonic reaction favors products endergonic reaction: a reaction in which the Gibbs free energy of the products is higher than that of the reactants; the position of equilibrium for an endergonic reaction favors starting materials
6-6
H 0<0
6-7
Energy Diagrams
x
Enthalpy change, 0 : the difference in total bond energy between reactants and products
a measure of bond making (exothermic) and bond breaking (endothermic)
Energy Diagrams
x
Energy diagram: a graph showing the changes in energy that occur during a chemical reaction Reaction coordinate: a measure in the change in positions of atoms during a reaction
6-9
Activation Energy
x
Transition state:
an unstable species of maximum energy formed during the course of a reaction a maximum on an energy diagram
Activation Energy, G: the difference in Gibbs free energy between reactants and a transition state
if G is large, few collisions occur with sufficient energy to reach the transition state; reaction is slow if G is small, many collisions occur with sufficient energy to reach the transition state; reaction is fast
6-10
Energy Diagram
a one-step reaction with no intermediate
6-11
Energy Diagram
x
6-12
How it is done
design experiments to reveal details of a particular chemical reaction propose a set or sets of steps that might account for the overall transformation a mechanism becomes established when it is shown to be consistent with every test that can be devised this does mean that the mechanism is correct, only that it is the best explanation we are able to devise
6-13
Why Mechanisms?
they are the framework within which to organize descriptive chemistry they provide an intellectual satisfaction derived from constructing models that accurately reflect the behavior of chemical systems they are tools with which to search for new information and new understanding
6-14
Electrophilic Additions
hydrohalogenation using HCl, HBr, HI hydration using H2O in the presence of H2SO4 halogenation using Cl2, Br2 halohydrination using HOCl, HOBr oxymercuration using Hg(OAc)2, H2O followed by reduction
6-15
Addition of HX
x
Carried out with pure reagents or in a polar solvent such as acetic acid
Br H H Br CH3 CH=CH2 Propene + HBr CH3 CH-CH2 + CH3 CH-CH2 2Bromopropane 1Bromopropane (notobserved)
Addition is regioselective
regioselective reaction: an addition or substitution reaction in which one of two or more possible products is formed in preference to all others that might be formed Markovnikovs rule: in the addition of HX, H2O, or ROH to an alkene, H adds to the carbon of the double bond having the greater number of hydrogens
6-16
HBr + 2-Butene
x
A two-step mechanism
Step 1: proton transfer from HBr to the alkene gives a carbocation intermediate slow,rate H + determining CH3 CH=CHCH3 + H Br CH3 CH-CHCH3 + Br secButylcation (a2carbocation intermediate) Step 2: reaction of the sec-butyl cation (an electrophile) with bromide ion (a nucleophile) completes the reaction + CH3CHCH2 CH3 Br Bromideion secButylcation (anucleophile) (anelectrophile) fast Br CH3CHCH2 CH3 2Bromobutane
6-17
HBr + 2-Butene
x
6-18
Carbocations
x
Carbocation: a species in which a carbon atom has only six electrons in its valence shell and bears positive charge Carbocations are classified as 1 , 2 , or 3 depending on the number of carbons bonded to the carbon bearing the positive charge electrophiles; that is, they are electron-loving Lewis acids
6-19
Carbocations
bond angles about a positively charged carbon are approximately 120 carbon uses sp2 hybrid orbitals to form sigma bonds to the three attached groups the unhybridized 2p orbital lies perpendicular to the sigma bond framework and contains no electrons
6-20
Carbocation Stability
a 3 carbocation is more stable than a 2 carbocation, and requires a lower activation energy for its formation a 2 carbocation is, in turn, more stable than a 1 carbocation, methyl and 1 carbocations are so unstable that they are never observed in solution
6-21
Carbocation Stability
relative stability
H H C+ H Methyl cation (methyl) CH3 H C+ CH3 CH3 C+ H Isopropyl cation (2) CH3 CH3 C+
Increasingcarbocationstability
methyl and primary carbocations are so unstable that they are never observed in solution
6-22
Carbocation Stability
we can account for the relative stability of carbocations if we assume that alkyl groups bonded to the positively charged carbon are electron releasing and thereby delocalize the positive charge of the cation we account for this electron-releasing ability of alkyl groups by (1) the inductive effect, and (2) hyperconjugation
6-23
6-24
Hyperconjugation
involves partial overlap of the -bonding orbital of an adjacent C-H or C-C bond with the vacant 2p orbital of the cationic carbon the result is delocalization of the positive charge
6-25
Addition of H2O
addition of water is called hydration acid-catalyzed hydration of an alkene is regioselective; hydrogen adds preferentially to the less substituted carbon of the double bond HOH adds in accordance with Markovnikovs rule
CH3CH=CH2 + H2O Propene
CH3 CH3C=CH2 + H2O 2Methylpropene
H2SO4
OH H CH3CH-CH2 2Propanol
H2SO4
6-26
Addition of H2O
Step 1: proton transfer from H3O+ to the alkene
CH3 CH=CH 2
+ +
H O H H
Step 2: reaction of the carbocation (an electrophile) with water (a nucleophile) gives an oxonium ion
CH3 CHCH 3
+ +
:O H H
:O-H H
fast
6-27
Carbocation Rearrangements
x
In electrophilic addition to alkenes, there is the possibility for rearrangement Rearrangement: a change in connectivity of the atoms in a product compared with the connectivity of the same atoms in the starting material
6-28
Carbocation Rearrangements
in addition of HCl to an alkene
Cl + HCl 3,3Dimethyl 1butene + Cl
OH
2Methyl2butanol
6-29
Carbocation Rearrangements
the driving force is rearrangement of a less stable carbocation to a more stable one
CH3 : : CH3 CCH=CH2 + H H 3Methyl1butene Cl: slow,rate determining CH3 H A2carbocation intermediate
+
CH3 C-CHCH3 + : Cl : :
the less stable 2 carbocation rearranges to a more stable 3 one by 1,2-shift of a hydride ion
CH3 CH 3 C-CHCH3
+
fast
Carbocation Rearrangements
reaction of the more stable carbocation (an electrophile) with chloride ion (a nucleophile) completes the reaction
CH 3 C- CH 2 CH 3 + : Cl : + CH 3
fast
CH 3 CH 3 C- CH 2 CH 3 : Cl :
: :
2-Chloro-2-methylbutane
6-31
Br2
CH2Cl2
Br Br CH3CH-CHCH3 2,3Dibromobutane
Br2
Br CH2 Cl2 +
Br
Cyclohexene
Br Br trans1,2Dibromocyclohexane (aracemicmixture)
addition occurs with anti stereoselectivity; halogen stereoselectivity atoms add from the opposite face of the double bond we will discuss this selectivity in detail in Section 6.7
6-32
Thesecarbocationsaremajor contributingstructures
Thebridgedbromonium ionretainsthegeometry
6-33
Br C Br Anti(coplanar)orientation ofaddedbromineatoms C C
Br
Br Newmanprojection oftheproduct Br
Br C C Br
-
Br C C Br Anti(coplanar)orientation ofaddedbromineatoms
Br Newmanprojection oftheproduct
6-34
+ Br2
Br Br
Br
Treatment of an alkene with Br2 or Cl2 in water forms a halohydrin Halohydrin: a compound containing -OH and -X on adjacent carbons
CH3CH=CH2 + Cl2 + H2O Propene HO Cl CH3CH-CH2 + HCl 1Chloro2propanol (achlorohydrin)
6-36
H H 2Bromo1methylcyclopentanol (aracemicmixture)
to account for the regioselectivity and the anti stereoselectivity, chemists propose the three-step mechanism in the next screen
6-37
Step 2: attack of H2O on the more substituted carbon opens the three-membered ring
: Br: H O: H H R C C H H H : H R : Br : C H C H H
6-38
: Br:
: Br : C C H H R H minorcontributing structure
C C H H R H bridgedbromonium ion
H R
Br C C H H
+ H3 O+
+
H
H H
O H
6-39
6-40
Oxymercuration/Reduction
x
reduction
OH HgOAc
NaBH4
OH H 2Pentanol
O + CH3COH + Hg Aceticacid
6-41
Oxymercuration/Reduction
an important feature of oxymercuration/reduction is that it occurs without rearrangement
1. Hg(OAc)2, H2 O 2. NaBH4 3,3Dimethyl1butene
OH 3,3Dimethyl2butanol
HgOAc
Cyclopentene
(Antiadditionof OHandHgOAc)
H H Cyclopentanol
6-42
Oxymercuration/Reduction
Step 1: dissociation of mercury(II) acetate
6-43
Oxymercuration/Reduction
Step 3: regioselective attack of H2O (a nucleophile) on the bridged intermediate opens the three-membered ring
6-44
Oxymercuration/Reduction
x
Anti stereoselective
we account for the stereoselectivity by formation of the bridged bromonium ion and anti attack of the nucleophile which opens the three-membered ring
Regioselective
of the two carbons of the mercurinium ion intermediate, the more substituted carbon has the greater degree of partial positive character alternatively, computer modeling indicates that the CHg bond to the more substituted carbon of the bridged intermediate is longer than the one to the less substituted carbon therefore, the ring-opening transition state is reached more easily by attack at the more substituted carbon
6-45
Hydroboration/Oxidation
x
6-46
Hydroboration/Oxidation
borane forms a stable complex with ethers such as THF the reagent is used most often as a commercially available solution of BH3 in THF
2
:O:
+ B2 H6
Tetrahydrofuran (THF)
6-47
Hydroboration/Oxidation
x
Hydroboration is both
regioselective (boron to the less hindered carbon) and syn stereoselective
+ H CH 3 BH 3 H BR 2 H3C H
1-Methylcyclopentene
6-48
Hydroboration/Oxidation
concerted regioselective and syn stereoselective addition of B and H to the carbon-carbon double bond
+ H B H CH3 CH2 CH2 CH=CH2 B CH3 CH2 CH2 CH-CH2
trialkylboranes are rarely isolated oxidation with alkaline hydrogen peroxide gives an alcohol and sodium borate
R3 B + H2 O2 + NaOH Atrialkyl borane 3ROH + Na3 BO3 Analcohol
6-49
Hydroboration/Oxidation
x
step 2: rearrangement of an R group with its pair of bonding electrons to an adjacent oxygen atom
R R B O O H R
+ O-H R B O
R
6-50
Hydroboration/Oxidation
step 3: reaction of the trialkylborane with aqueous NaOH gives the alcohol and sodium borate
(RO)3 B + 3NaOH Atrialkylborate 3ROH + Na3 BO3 Sodiumborate
6-51
Oxidation/Reduction
x
Recognize using a balanced half-reaction 1. write a half-reaction showing one reactant and its product(s) 2. complete a material balance; use H2O and H+ in acid solution, use H2O and OH- in basic solution 3. complete a charge balance using electrons, e6-52
Oxidation/Reduction
three balanced half-reactions
OH CH3 CH=CH2 + H2 O Propene CH3 CHCH3 2Propanol HO OH CH3 CH=CH2 + 2H2 O Propene CH3 CH=CH2 + 2H+ + 2ePropene CH3 CHCH2 + 2H+ + 2e1,2Propanediol CH3 CH2 CH3 Propane
6-53
OsO4 oxidizes an alkene to a glycol, a compound glycol with OH groups on adjacent carbons
oxidation is syn stereoselective
OsO4 O O Os O O Acyclicosmate NaHSO3 H2O OH
OH cis1,2Cyclopentanediol (acisglycol)
6-54
6-55
Oxidation with O3
x
Treatment of an alkene with ozone followed by a weak reducing agent cleaves the C=C and forms two carbonyl groups in its place
CH3 CH3 C=CHCH 2 CH 3 2-Methyl-2-pentene 1. O3 CH3 CCH 3 2. (CH3 ) 2 S Propanone (a ketone) O O + HCCH 2 CH3 Propanal (an aldehyde)
6-56
Oxidation with O3
the initial product is a molozonide which rearranges to an isomeric ozonide
CH 3 CH=CH CH 3 2-Butene O3 O OO CH 3 CH-CHCH 3 A molozonide H H3 C O H O CH 3 CH
6-57
Reduction of Alkenes
x
Most alkenes react with H2 in the presence of a transition metal catalyst to give alkanes
+ H2 Cyclohexene Pd 25 C, 3 atm Cyclohexane
commonly used catalysts are Pt, Pd, Ru, and Ni the process is called catalytic reduction or, alternatively, catalytic hydrogenation addition occurs with syn stereoselectivity
6-58
Reduction of Alkenes
x
6-59
Reduction of Alkenes
even though addition syn stereoselectivity, some product may appear to result from trans addition
CH3 CH3 1,2Dimethyl cyclohexene H2 / Pt CH3
+
reversal of the reaction after the addition of the first hydrogen gives an isomeric alkene, etc.
CH3 CH3 1,2Dimethyl cyclohexene H2/ Pt H CH3 H Pt HCH3 CH3 CH3 1,6Dimethyl cyclohexene
6-60
H0 of Hydrogenation
x
6-61
H0 of Hydrogenation
Name Ethylene Propene 1Butene cis2Butene trans2Butene 2Methyl2butene 2,3Dimethyl2butene Structural Formula CH2 =CH2 CH3 CH=CH2 H [kJ(kcal)/m ol] 137(32.8) 126(30.1) 127(30.3) 120(28.6) 115(27.6) 113(26.9) 111(26.6)
6-62
Reaction Stereochemistry
x
In several of the reactions presented in this chapter, chiral centers are created Where one or more chiral centers are created, is the product
one enantiomer and, if so, which one? a pair of enantiomers as a racemic mixture? a meso compound? a mixture of stereoisomers?
As we will see, the stereochemistry of the product for some reactions depends on the stereochemistry of the starting material; that is, some reactions are stereospecific
6-63
Reaction Stereochemistry
x
Br2
CH2Cl2
Br Br CH3CH-CHCH3 2,3Dibromobutane
two stereoisomers are possible for 2-butene; a pair of cis,trans isomers three stereoisomers are possible for the product; a pair of enantiomers and a meso compound if we start with the cis isomer, what is the stereochemistry of the product? if we start with the trans isomer, what is the stereochemistry of the product?
6-64
Bromination of cis-2-Butene
reaction of cis-2-butene with bromine forms bridged bromonium ions which are meso and identical
6-65
Bromination of cis-2-Butene
attack of bromide ion at carbons 2 and 3 occurs with equal probability to give enantiomeric products as a racemic mixture
6-66
Bromination of trans-2-Butene
reaction with bromine forms bridged bromonium ion intermediates which are enantiomers
6-67
Bromination of trans-2-Butene
attack of bromide ion in either carbon of either enantiomer gives meso-2,3-dibromobutane
6-68
Bromination of 2-Butene
x
Given these results, we say that addition of Br2 or Cl2 to an alkene is stereospecific
bromination of cis-2-butene gives the enantiomers of 2,3-dibromobutane as a racemic mixture bromination of trans-2-butene gives meso-2,3dibromobutane
Stereospecific reaction: a reaction in which the stereochemistry of the product depends on the stereochemistry of the starting material
6-69
Oxidation of 2-Butene
OsO4 oxidation of cis-2-butene gives meso-2,3butanediol H H
H3C C H H3 C C
2 3 2 3
CH3
OsO4 ROOH
HO OH (2S,3R)2,3Butanediol HO OH C
2 3
H H CH3 H3 C (2R,3S)2,3Butanediol
6-70
Oxidation of 2-Butene
x
H3 C H trans2Butene (achiral)
CH3
OsO4 ROOH
HO OH (2S,3S)2,3Butanediol HO OH C
2 3
CH3 H H H3 C (2R,3R)2,3Butanediol
6-71
Reaction Stereochemistry
x
We have seen two examples in which reaction of achiral starting materials gives chiral products
in each case, the product is formed as a racemic mixture (which is optically inactive) or as a meso compound (which is also optically inactive)
These examples illustrate a very important point about the creation of chiral molecules
optically active (enantiomerically pure) products can never be produced from achiral starting materials and achiral reagents under achiral conditions although the molecules of product may be chiral, the product is always optically inactive (either meso or a pair of enantiomers)
6-72
Reaction Stereochemistry
x
Next let us consider the reaction of a chiral starting material in an achiral environment
the bromination of (R)-4-tert-butylcyclohexene only a single diastereomer is formed
Br2 Br Br redrawas achair conformation Br Br
(R)4tertButyl cyclohexene
(1S,2S,4R)1,2Dibromo4tertbutylcyclohexane
the presence of the bulky tert-butyl group controls the orientation of the two bromine atoms added to the ring
6-73
Reaction Stereochemistry
x
6-74
Reaction Stereochemistry
treating (R)-BINAP with ruthenium(III) chloride forms a complex in which ruthenium is bound in the chiral environment of the larger BINAP molecule this complex is soluble in CH2Cl2 and can be used as a homogeneous hydrogenation catalyst
(R)BINAP + RuCl3 (R)BINAPRu
6-75
Reaction Stereochemistry
BINAP-Ru complexes are somewhat specific for the types of C=C they reduce to be reduced, the double bond must have some kind of a neighboring group that serves a directing group
(S)BINAPRu OH H2 OH
(R)3,7Dimethyl6octen1ol (R)BINAPRu OH
(E)3,7Dimethyl2,6octadien1ol (Geraniol)
(S)3,7Dimethyl6octen1ol
6-76
Reactions of Alkenes
End Chapter 6
6-77